CN101824115B - One-step method for synthesizing styrene/ N-benzyl maleimide/ maleic anhydride terpolymer - Google Patents
One-step method for synthesizing styrene/ N-benzyl maleimide/ maleic anhydride terpolymer Download PDFInfo
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- CN101824115B CN101824115B CN200910046948XA CN200910046948A CN101824115B CN 101824115 B CN101824115 B CN 101824115B CN 200910046948X A CN200910046948X A CN 200910046948XA CN 200910046948 A CN200910046948 A CN 200910046948A CN 101824115 B CN101824115 B CN 101824115B
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Abstract
The invention belongs to the technical field of macromolecular heat-resistant impact modifiers, and relates to a one-step method for synthesizing a styrene/ N-benzyl maleimide/ maleic anhydride terpolymer. The method prepares the terpolymer by adopting a solvent polymerization one-time feeding method; the chemical structure of the related heat-resistant impact modifier is the terpolymer of N-benzyl maleimide, styrene and maleic anhydride; the molar ratio of the N-benzyl maleimide to the styrene is 1: 1-1: 2, and the content of the maleic anhydride is 1.8 to 2.6 percent; and the terpolymer represents a single glass-transition temperature. The method can solve the integrated problems of complex equipment, complex process, instable quality and the like in the prior art. The method has the characteristics of simple preparation, short reaction time, low equipment investment and high economic return.
Description
Technical field
The invention belongs to the heat-resisting resistance properties-correcting agent of polymer technical field, relate to a kind of preparation method of multipolymer, relate in particular to the method for single stage method synthesizing styrene/N-phenylmaleimide/maleic anhydride terpolymer.
Background technology
The thermotolerance that prior art discloses macromolecular material is an importance of its performance, and the acid imide polymkeric substance is subjected to common concern with its superior resistance toheat.The N-phenylmaleimide conduct is a member wherein, is a kind of novel stable on heating monomer of developing in recent years of resin that improves.Vinylbenzene/N-phenylmaleimide/maleic anhydride terpolymer (St/N-PMI/MAH) is owing to introduced N-phenylmaleimide (N-PMI) and maleic anhydride (MAH), imide ring-type structure increases in the molecular chain, maleic anhydride chemical reaction grafting functional group introduces, the resistance toheat of polymkeric substance is significantly improved, and have and polyamide-based, polystyrene type, macromolecular material molten chemical grafting abilities such as PVC class are a kind of good heat-resisting graft modification agent.The St/N-PMI/MAH multipolymer is at modifying plastics and preparation special plastic alloy wide application prospect to be arranged.
At present synthetic St/N-PMI/MAH multipolymer mainly adopts body dilution polymeric mode, have following deficiency and defective: molecular weight increases in the bulk polymerisation process, polymerization viscosity increases suddenly, heat of polymerization is difficult to be delivered to the external condensation device by polymerisate, reaction control is complicated, even if adopt the dropping feeding manner to improve polymerization technique, but because the speed that drips is slow, the time that drips is too long, therefore the fluctuation of the product structure of mass polymerization composition is very big, thereby has influenced the physicals of product.So, adopt body dilution mode to prepare the St/N-PMI/MAH terpolymer, cause equipment cost huge, complex process has greatly influenced the expansion of product output.
Summary of the invention
The present invention seeks in order to overcome the deficiencies in the prior art, a kind of high N-phenylmaleimide content chemical graft response type compatilizer and preparation method thereof is provided, is specifically related to the method for a kind of employing solution polymerization, single stage method synthesizing styrene/N-phenylmaleimide/maleic anhydride terpolymer (St/N-PMI/MAH).
Particularly, the present invention adopts feeding method of solvent polymeric to prepare terpolymer, the chemical structure that the heat-proof impact-resistant that relates to hits agent is the terpolymer of N-phenylmaleimide, vinylbenzene, maleic anhydride, N-phenylmaleimide and cinnamic mol ratio are 1 in the described terpolymer: 1-1: 2, maleic anhydride content is 1.8%-2.6%, and product shows the single glass transition temperature.Present method can solve the equipment complexity of prior art, complex process, composition problems such as quality instability.
The inventive method is by following step,
Load onto airway respectively at 500ml four-hole reactor, reflux condensate device, whipping appts, thermometer feeds nitrogen earlier, blow out residual air in the reactor, mixing raw material and high boiling solvent are added, and wherein mixing raw material and solvent adding mode can be divided into: earlier mixing raw material is stirred formation homogeneous phase mixed solution by fusion under 60-80 ℃ of normal pressure, in the example of the present invention, pressure 101.3KPa stir 40-60 minute fully dissolving form mixed solution, import polymerization in the solvent of preheating then; Or directly mixing raw material and solvent are added reactor, and be warming up to 60-80 ℃ under nitrogen protection and mechanical stirring, form mixing solutions, carry out solution polymerization; Heat temperature raising drops into initiator under 90-100 ℃, be warming up to 120-150 ℃, and it is constant to keep-up pressure, and reacts 0.5-6 hour, after reaction is finished, and the constant boiling that is warming up to that keep-ups pressure, solvent evaporated, cooling is again filtered, and drying obtains finished product.
Described mixing raw material is vinylbenzene, N-phenylmaleimide and maleic anhydride, and its mass percent consists of: N-phenylmaleimide 25-50%; Vinylbenzene 45-70%; Maleic anhydride 1-5%.
Described high boiling solvent is selected from ketone, amides, sulfoxide class and benzene class such as pimelinketone, dimethyl formamide, dimethylbenzene, dimethyl sulfoxide (DMSO) etc.Solvent boiling point is greater than 120 ℃; The quality of solvent is 0.8-4 a times of mixing raw material quality.
Described initiator can be organo-peroxide or azo compound, and organo-peroxide comprises organic ketone peroxide class, ketal peroxide class, superoxide, dialkyl class, peroxidation diacrylate class, peroxyester, peroxy dicarbonates.As the peroxidation neighbour (to) phthalic acid dibutyl ester, benzoyl peroxide.Azo class organic compound has azo dicyclohexyl formonitrile HCN, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile).Described initiator amount accounts for the 0.01%-2% of mixed solution total mass.
Among the present invention, in every 100g mixing raw material, initiator amount is 0.1-2g, solvent load 80-400g.
The present invention adopts the solution polymerization mode to synthesize the multipolymer of St/N-PMI/MAH, can directly obtain powdery product, and synthesis technique is simple, reaction times is short, and facility investment is little, after reaction finishes, only need be warming up to boiling, more after filtration, dry, can obtain final product.Owing to adopt " single stage method " can obviously reduce the synthetic cost, simplify technology, prepared multipolymer has good thermotolerance and chemically reactive, can be used as polystyrene type, nylon-type, ester plastic modification and PC/ABS alloy A BS class heat-proof impact-resistant hit properties-correcting agent.The present invention possesses the high characteristics of economy return, is fit to large-scale the popularization.
Description of drawings
Fig. 1 is the infrared spectrum of vinylbenzene/N-PMI/MAH terpolymer.
Fig. 2 vinylbenzene/N-PMI/MAH
1The H nmr spectrum.
Fig. 3 vinylbenzene/N-PMI/MAH liquid phase gel chromatography.
Fig. 4 vinylbenzene/N-PMI/MAH weight-loss curve spectrogram.
Embodiment
Embodiment 1
15g N-PMI, 34g St, 1g MAH and 136mL xylene solvent are joined in the 500mL reactor, feed nitrogen, blow out air residual in the reactor, be warming up to about 76 ℃, stir 40-60min and form homogeneous phase solution, be rapidly heated then about 95 ℃, input 0.25g peroxidation neighbour (to) phthalic acid dibutyl ester, the limit coronite is warmed up to about 125 ℃, and constant reaction 4h keep-ups pressure.Reaction is warming up to explosive evaporatoin and falls residual solvent and monomer after finishing, and obtains pale yellow powder shape product after considering drying.
From Fig. 1 vinylbenzene/N-PMI/MAH terpolymer infrared spectrum, can obtain as drawing a conclusion in the contrast of polystyrene and vinylbenzene/N-PMI/MAH spectral line: 1777cm
-1And 1712cm
-1Be respectively the carboxyl charateristic avsorption band of maleic anhydride and N phenyl maleimide, 1454cm
-1, 1495cm
-1Phenyl ring absorption peak and 1383cm
-1Be imide five-ring absorption peak, 1184cm
-1Be C-N key charateristic avsorption band in the imide, be positioned at 748cm in addition
-1And 698cm
-1It is the C-H out-of-plane deformation vibration absorption peak on the phenyl ring in styrene units and the N-phenylmaleimide unit.1184cm
-1, 1383cm
-1, 1712cm
-1Three place's charateristic avsorption bands illustrate and contain the N-phenylmaleimide structural unit in the polymerization sample.
From Fig. 2 vinylbenzene/N-PMI/MAH terpolymer
1The H nmr spectrum obtains the δ (chemical shift) of the H of vinylbenzene methylene radical and methyne at 1-2.4ppm, the δ of NPMI unit methyne H is at 2.4-4.0ppm, the δ of H in the styrol structural unit in the phenyl ring at 6-7.2ppm and in the NPMI structural unit δ of the H in the phenyl ring at 7.21-8.0ppm, and the chemical shift of the δ of H H in 3-4ppm and NPMI modular construction is overlapping in the MAH structural unit, by recording MAH content according to the GB/T601-2002 acid base titration.Concrete data are as follows:
Chemical displacement value from figure and integral area thereof can draw the content of N-PMI in the product about 52%.The content of MAH is about 2%, and St content is about 46%.
Fig. 3 is the liquid phase gel chromatography of vinylbenzene/N-PMI/MAH.Record the M of terpolymer with polystyrene standards
wBe about 4.5 ten thousand, M
w/ M
nBe 2.21
Fig. 4 is vinylbenzene/N-PMI/MAH weight-loss curve spectrogram, records terpolymer extension initial decomposition temperature (T
d) be 395.4 ℃, weightless 20% and weightless 50% temperature be respectively 397.8 ℃ and 416.5 ℃, the standard heat decomposition temperature of trying to achieve the St/N-PMI/MAH terpolymer with these 2 intersection points of doing the extended line of straight line and baseline according to international standard office (ISO) is 385.1 ℃
Embodiment 2
20g N-PMI, 29g St, 1g MAH and 136mL xylene solvent are joined in the 500mL reactor, feed nitrogen, blow out air residual in the reactor, be warming up to about 76 ℃, stir 40-60min and form homogeneous phase solution, be rapidly heated then about 95 ℃, input 0.25g peroxidation neighbour (to) phthalic acid dibutyl ester, the limit coronite is warmed up to about 125 ℃, and constant reaction 4h keep-ups pressure.Reaction is warming up to explosive evaporatoin and falls residual solvent and monomer after finishing, and obtains pale yellow powder shape product after considering drying.
Embodiment 3
25g N-PMI, 24g St, 1g MAH and 136mL xylene solvent are joined in the 500mL reactor, feed nitrogen, blow out air residual in the reactor, be warming up to about 76 ℃, stir 40-60min and form homogeneous phase solution, be rapidly heated then about 95 ℃, input 0.25g peroxidation neighbour (to) phthalic acid dibutyl ester, the limit coronite is warmed up to about 125 ℃, and constant reaction 4h keep-ups pressure.Reaction is warming up to explosive evaporatoin and falls residual solvent and monomer after finishing, and obtains pale yellow powder shape product after considering drying.
Embodiment 4
15g N-PMI, 34g St, 1g MAH and 136mL xylene solvent are joined in the 500mL reactor, feed nitrogen, blow out air residual in the reactor, be warming up to about 76 ℃, stir 40-60min and form homogeneous phase solution, be rapidly heated then about 95 ℃, input 0.375g peroxidation neighbour (to) phthalic acid dibutyl ester, the limit coronite is warmed up to about 125 ℃, and constant reaction 4h keep-ups pressure.Reaction is warming up to explosive evaporatoin and falls residual solvent and monomer after finishing, and obtains pale yellow powder shape product after considering drying.
Embodiment 5
15g N-PMI, 34g St, 1g MAH and 136mL xylene solvent are joined in the 500mL reactor, feed nitrogen, blow out air residual in the reactor, be warming up to about 76 ℃, stir 40-60min and form homogeneous phase solution, be rapidly heated then about 95 ℃, input 0.50g peroxidation neighbour (to) phthalic acid dibutyl ester, the limit coronite is warmed up to about 125 ℃, and constant reaction 4h keep-ups pressure.Reaction is warming up to explosive evaporatoin and falls residual solvent and monomer after finishing, and obtains pale yellow powder shape product after considering drying.
Embodiment 6
15g N-PMI, 34g St, 1g MAH and 136mL xylene solvent are joined in the 500mL reactor, feed nitrogen, blow out air residual in the reactor, be warming up to about 76 ℃, stir 40-60min and form homogeneous phase solution, be rapidly heated then about 95 ℃, input 0.75g peroxidation neighbour (to) phthalic acid dibutyl ester, the limit coronite is warmed up to about 125 ℃, and constant reaction 4h keep-ups pressure.Reaction is warming up to explosive evaporatoin and falls residual solvent and monomer after finishing, and obtains pale yellow powder shape product after considering drying.
Embodiment 7
15g N-PMI, 34g St, 1g MAH and 136mL xylene solvent are joined in the 500mL reactor, feed nitrogen, blow out air residual in the reactor, be warming up to about 76 ℃, stir 40-60min and form homogeneous phase solution, be rapidly heated then about 95 ℃, input 1g peroxidation neighbour (to) phthalic acid dibutyl ester, the limit coronite is warmed up to about 125 ℃, and constant reaction 4h keep-ups pressure.Reaction is warming up to explosive evaporatoin and falls residual solvent and monomer after finishing, and obtains pale yellow powder shape product after considering drying.
Physicals
The St/N-PMI/MAH terpolymer of embodiment 1,2,3,4,5,6,7 preparation is carried out infrared, nucleus magnetic resonance, acid base titration, the test of liquid phase gel chromatography, every index and result are as follows:
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| The N-PMI massfraction | 52％ | 60％ | 63％ | 52％ | 52％ | 52％ | 52％ |
| Second-order transition temperature/℃ | 193.3-202 .6 | 206.3-212 .3 | 214.8-216 .8 | 193.3-202 .6 | 193.3-202 .6 | 193.3-202 .6 | 193.3-202 .6 |
| MAH content | 1.85-2.16 ％ | 1.85-2.16 ％ | 1.85-2.16 ％ | 1.85-2.16 ％ | 1.85-2.16 ％ | 1.85-2.16 ％ | 1.85-2.16 ％ |
| GPC/10 4 | 4.55 | 5.19 | 6.89 | 3.83 | 3.18 | 2.21 | 2.00 |
 |
2.21 | 2.32 | 2.75 | 2.07 | 2.15 | 2.14 | 2.12 |
| The standard heat decomposition temperature/℃ | 385.1 | 394.5 | 395.2 | 384.8 | 386.2 | 388.5 | 387.8 |
| Productive rate/% | 85 | 80 | 82 | 84 | 88 | 86 | 87 |
By the data in the table as can be seen, the second-order transition temperature of multipolymer, dispersion coefficient, heat decomposition temperature etc. embody its resistance toheat all along with the increase of the content of the N-PMI of multipolymer and raise, the resistance toheat that is multipolymer improves along with the increase of its N-PMI content, can select different N-PMI content and different molecular weight terpolymer to hit agent as heat-proof impact-resistant according to different resin modified demands.
Claims (8)
1. the method for single stage method synthesizing styrene/N-phenylmaleimide/maleic anhydride terpolymer is characterized in that: at 60-80 ℃, pressure 101.3KPa stirs dissolving in 40-60 minute and forms mixed solution with mixing raw material, add solvent then, keep normal pressure, be warming up to 90-100 ℃, add initiator, be warming up to 120-150 ℃ once more, keep-up pressure with temperature-resistant, reacted 0.5-6 hour, after reaction is finished, the constant boiling that is warmed up to that keep-ups pressure, cooling again, filter the dry finished product that gets; Described mixing raw material is vinylbenzene, N-phenylmaleimide and maleic anhydride, and its mass percent consists of: N-phenylmaleimide 25-50%; Vinylbenzene 45-70%; Maleic anhydride 1-5%;
Described initiator amount accounts for the 0.01%-2% of mixed solution total mass.
2. method according to claim 1 is characterized in that: described solvent is a high boiling solvent, and solvent boiling point is greater than 120 ℃; The quality of solvent is 0.8-4 a times of mixing raw material quality.
3. method according to claim 1 and 2 is characterized in that: described solvent is selected from ketone, amides, sulfoxide class or benzene class.
4. method according to claim 1 and 2 is characterized in that: described solvent is selected from pimelinketone, dimethyl formamide, dimethylbenzene or dimethyl sulfoxide (DMSO).
5. method according to claim 1 is characterized in that: described initiator is organo-peroxide or azo compound.
6. method according to claim 5 is characterized in that: described organo-peroxide is selected from organic peroxy ketone, ketal peroxide class, dialkyl class, peroxidation diacrylate class, peroxyester or peroxy dicarbonates.
7. method according to claim 6 is characterized in that: described organo-peroxide is selected from peroxidation dibutyl phthalate, peroxidation dibutyl terephthalate or benzoyl peroxide.
8. method according to claim 5 is characterized in that: described azo compound is selected from azo dicyclohexyl formonitrile HCN, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
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